DE69530455T2 - Active radiation curable composition for recording medium, and imaging method using the same - Google Patents

Description

The present invention relates to a new composition, which by active energy rays curable and a recording medium using the same. In particular The present invention relates to a composition which is suitable for forming an ink receiving layer which is a high absorbency for on Shows water-based ink and high durability, a recording medium, which is formed using the ink receiving layer, and an image forming method using the recording medium.

Jet recording systems have been among digital recording systems in recent years made rapid progress, and are widely used as the output system for PC's in offices been used. The widespread use of ink jet recording systems results from the development of small but multi-nozzle ink jet recording heads high density, development of a precise drive technology for this, and development of recording media for high-resolution Picture quality. Most of the inkjet printing systems used in practice use inks that mainly are composed of water. Water based ink is at the office and industrial use in view of environmental protection and Human health security desirable.

Problems still arise with conventional ones Recording media such as ink jet recording paper sheets and Overhead projector films that are suitable for printers that use a water-based ink. First, ink jet recording paper sheets are included water justice is insufficient because they tend to be a Bleeding by diffusion of a dye in the water-based Ink on the paper sheet under high humidity conditions to cause. Second, overhead projector films themselves are included insufficient of water justice and do not give a picture water justice, and special care should be taken with the use and storage of Overhead projector films can be used.

The above problems will through a water soluble Polymer that gives high absorbency for on Water-based ink is built into the recording medium, caused. It has been believed that both in ink based recording paper sheets as well as in the overhead projector films a water fastness of the recording medium for a water-based Ink inevitably with an ink receiving property and an ink absorbency would not be compatible.

On the other hand, the inkjet printer used industrially as a digital printing device. In such In industrial applications, there is often a case that the Recording media no absorbing capacity Have water-based ink. For such recording media it is necessary to temporarily apply an ink receiving layer a recording medium in the case of using one on water based ink. For industrial uses various recording media including metal plates, plastics, Rubber, ceramics, fabrics, leather, glass and food packaging materials used. The specific examples are prepaid cards, compact disks, laser disks, name plates, image displays, image formation on an FRP plate and on a porcelain plate, textile printing, coloring of Leather, formation of dyed Glass, reproduction of pictures and paintings etc. Most of the Base materials for the above uses obviously have no absorbency for on Water based inks.

Easy application of a conventional one Coating material on coated paper sheets and Overhead projector films for However, ink jet printing is in practice for making the above mentioned industrial print media insufficient, mainly because the coating materials are inadequate when attached and the suitability for coating on different base materials, Shelf life and waterfastness of the coating films, waterfastness of the formed image, resistance to scratching, etc.

In the above industrial Applications must be the coating material for the ink receiving layer additionally to a sufficient coloring ability having properties such as (1) formation of an ink receiving layer in a short time, (2) high adhesion of the layer formed to the base material, (3) fixation of the ink in a short time, (4) high affinity with coloring Matter (dye or pigment) in the ink, (5) formation of sharp High resolution images, (6) high durability of the resin layer, etc.

Conventional materials for the ink receiving layer inkjet recording are in their performance at industrial Inadequate uses and can therefor Not used.

In order to meet the above properties (1) to (6), techniques have been disclosed in which an ink-receiving layer for ink jet recording is formed by ultraviolet curing (for example, Japanese Patent Application Publication No. 1-286 886). However, the ink-receiving layers formed of a conventional water-soluble acrylic ester type photopolymerizable monomer do not meet the above-mentioned requirements, particularly high inks sorbability, a high ink absorption rate, and full affinity for coloring matter, and are therefore not suitable for ink jet recording printers developed in recent years.

EP-A-0 580 030 discloses a thermoplastic Resin with a coated layer on it, which is a quaternary ammonium salt Copolymer comprising structural units (a) and (b) in a specific weight ratio includes. Monomer unit (a) can be made from (meth) acrylate compounds, which is modified by a hydroxypropyltrialkylammonium chloride compound are derived. Monomer unit (b) contains alkyl (meth) acrylate. Such thermoplastic resins can be improved antistatic Properties and prevention of ink drawing and improvement of ink transfer when used as a synthetic paper.

EP-A-0 213 317 discloses base catalyzed Low-temperature, self-crosslinking polymers that consist of a halohydrin monomer unit, a tertiary or secondary Amine salt monomer unit and a vinyl polymerizable monomer unit exist for electroconductive coatings for Paper substrates can be used.

The present invention intends to provide a composition curable by active energy rays, an ink receiving layer having the above properties (1) to (6) form, in particular, a high absorbency for one water based ink and a high affinity for one coloring Owns matter.

The present invention is intended furthermore, a recording medium having one of the above composition formed ink receiving layer and a method of manufacturing to provide the recording medium.

The present invention is intended further, a method of image formation with high durability of the formed Image.

The above goals can be achieved by the present invention can be achieved.

worin Z₁ bis Z₆ unabhängig einen Rest darstellen, der von einem mehrwertigen Alkohol oder einem Polyepoxid abgeleitet ist, K₁ unabhängig einen Rest der Formel

darstellen,
jedes von K₂ einen Rest der Formel

darstellt,
R₁ unabhängig darstellt:

worin R₃ unabhängig H- oder CH₃- ist, und
R₂ unabhängig einen Rest der Formel CH₂=CHCOO-, oder CH₂=C(CH₃)COO- darstellt.According to the present invention, there is provided a composition curable by active energy rays of the present invention comprising a cationic polyacryloyl compound having two or more acryloyl groups and one or more cationic groups in one molecule, represented by any of the general formulas (1) to ( 6) and (2-1), (2-3) and (2-6):

wherein Z ₁ to Z ₆ independently represent a radical which is derived from a polyhydric alcohol or a polyepoxide, K ₁ independently represents a radical of the formula

represent
each of K _{2 is} a residue of the formula

represents,
R ₁ independently represents:

wherein R _{3 is} independently H- or CH ₃ -, and
R ₂ independently represents a radical of the formula CH ₂ = CHCOO-, or CH ₂ = C (CH ₃ ) COO-.

According to the present invention there is further provided a recording medium comprising a base material and an ink receiving layer formed thereon, in which the ink-receiving layer is a cationic polyacryloyl compound polymer with two or more acryloyl groups and one or more cationic Groups in one molecule comprises, by any of the general formulas above (1) to (6) is shown.

According to the present invention becomes a method of manufacturing a recording medium provided, which comprises: applying an active energy beam curable Composition on a base material, which is a cationic polyacryloyl compound with two or more acryloyl groups and one or more cationic Groups in one molecule comprises, by any of the general formulas above (1) to (6) and irradiating the composition with active energy rays.

Description of the preferred embodiments The inventors of the present invention have the compositional Material for examines a recording layer used for ink jet recording a water-based ink is used, in particular those for Inkjet color printers are suitable, which in recent years have been increasingly used and the above requirements (1) to (6), especially a high absorbency for a water-based Ink with a high absorption rate and a high affinity for one discoloring Show matter. As the results, they found that the cationic acryloyl compounds by the above general formulas (1) to (6) are shown, sufficient Show effects and many of the needed Fulfill properties, and completes the present invention.

The present invention relates to a material which can be hardened by active energy rays, in particular by ultraviolet rays or UV rays. The two or more acryloyl groups in the compounds of the general formulas (1) to (6) show a hardening function by an action of UV rays, and the one or more cationic groups of these compounds serve as the fixing site for a dye or a pigment dispersion. The synergistic functions lead to that the composition containing the above compound of the present invention forms an ink receiving layer which is practically fixed in a short time by irradiation with active energy rays such as ultraviolet rays and electron beams after application to a base material and is excellent in dye fixing.

The present invention is as follows in greater detail to be discribed.

The basic component that makes up the composition of the present invention is a cationic polyacryloyl compound which by any of the above general formulas (1) to (6), the two or more acryloyl groups and possess one or more cationic groups in the molecule. For example, the connection can be made by any of the following Synthesis routes are made.

Synthesis route 1:

A polyepoxide with two or more epoxy groups is reacted with an acrylic monomer with a tertiary amino group:

Synthesis route 2:

At least one of n epoxy groups (n ≥ 3) of a polyepoxide is reacted with a trialkylamine, such as trimethylamine, to introduce a cationic group, to cationize it (cationization), and then the remaining m epoxy groups (m ≥ 2) with (meth -) implemented acrylic acid:

Synthesis route 3:

At least one of k acryloyl groups (k ≥ 3) of a photopolymerizable polyacryloyl compound is reacted with trimethylamine or the like by Michael addition reaction to cationize it and form a compound with h acryloyl groups (h ≥ 2) and (kh) cationic groups:

Synthesis route 4:

At least one hydroxyl group of a polyacryloyl compound with one or more hydroxyl groups is reacted with a cationizing agent (cation-introducing agent):

A suitable synthesis route can considering the structure and purity of the starting material and the structure the intended connection.

Examples of the polyepoxides used in synthesis routes 1 and 2 are shown below:

In principle, the compounds of the general formulas (1) to (6) can also be synthesized from many polyglycidyl compounds which differ from those shown above and which have more glycidyl groups. Commercially available polyfunctional epoxies are exemplified by: DENAKOL EX-810, DENAKOL EX-811, DENAKOL EX-851, DENAKOL EX-830, DENAKOL EX-832, DENAKOL EX-841, DENAKOL EX-861, DENAKOL EX-911, DENAKOL EX-941, DENAKOL EX-920, DENAKOL EX-921, DENAKOL EX-931, DENAKOL EX-211, DENAKOL EX-212, DENAKOL EX-221, DENAKOL EX-721, DENAKOL EX-313, DENAKOL EX-321 (trade names, manufactured by Nagase Kasei Kogyo KK).

Examples of an acrylic monomer having a tertiary amino group used in Synthesis Route 1 are shown below:
N, N-dimethylaminoethyl methacrylate (CH ₂ = C (CH ₃ ) -COO-CH ₂ CH ₂ N (CH ₃ ) ₂ ),
N, N-dimethylaminoethyl acrylate (CH ₂ = CH-COO-CH ₂ CH ₂ N (CH ₃ ) ₂ ),
N, N-dimethylamainopropyl methacrylate (CH ₂ = C (CH ₃ ) -COO-CH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ ),
N, N-dimethylaminopropyl acrylate (CH ₂ = CH-COO-CH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ ),
N, N-dimethylacrylamide (CH ₂ = CH-CON (CH ₃ ) ₂ ),
N, N-dimethyl methacrylamide (CH ₂ = C (CH ₃ ) -CON (CH ₃ ) ₂ ),
N, N-dimetyhlaminoethyl acrylamide (CH ₂ = CH-CONHCH ₂ CH ₂ N (CH ₃ ) ₂ ),
N, N-dimethylaminoethyl methacrylamide (CH ₂ = C (CH ₃ ) -CONHCH ₂ CH ₂ N (CH ₃ ) ₂ ),
N, N-dimethylaminopropylacrylamide (CH ₂ = CH-CONHCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ ),
N, N-dimethylaminopropyl methacrylamide (CH ₂ = C (CH ₂ ) -CONHCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ ),
3-N, N-dimethylamino-2-hydroxypropylacrylamide (CH ₂ = CH-CONHCH ₂ CH (OH) CH ₂ N (CH ₃ ) ₂ ),
3-N, N-Dimethylamino-2-hydroxypropyl methacrylamide (CH ₂ = C (CH ₃ ) -CONHCH ₂ CH (OH) CH ₂ N (CH ₃ ) ₂ ).

The connections with three or more Acryloyl groups in the molecule, used in Synthesis Route 3 include (meth) acrylate esters polyols with three or more hydroxyl groups, such as trimethylolpropane triacrylate; (Meth) acrylate esters of polyepoxides with three or more epoxy groups. The mentioned above Polyols with three or more hydroxyl groups include glycerol, Trimethylolpropane, pentaerythritol, dipentaerithritol, polyglycerol, 1,2,6-hexanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 1,2,4-butanetriol, tri (hydroxyethyl) isocyanurate, Sugar alcohols and the like.

The polyacryloyl compounds with one or more hydroxyl groups used in route 4 of the synthesis are partial (meth) acrylate esters of the above polyols, and (meth) acrylate esters of the above polyglycidyl ethers (epoxy acrylates of a photopolymerizable oligomer as commercial products). The cationizing agent used in Synthesis Route 4 includes Compounds with both a glycidyl group and a cationic Group such as Wisetecks E-100, Wisetecks N-50 and the like (trade name, manufactured by Nagaase Kasei K.K.).

Furthermore, the connection of the general Formulas (1) to (6) can be synthesized by a route in which a compound with two or more halomethyl groups on the Ends of the molecule with a tertiary Amine monomer is implemented. However, since some types of connections with two or more halomethyl groups at the ends of the molecule too commercially available the above water-soluble polyepoxides are useful used.

Examples of the synthesis routes given above 1 to 4 synthesized and useful in the present invention Connections are shown below.

For synthesis route 1:

For synthesis route 2:

For Synthesis route 3:

For synthesis route 4:

Typical chemical formulas of preferred Compounds are there in the present invention under the mentioned above six general formulas and the above four synthesis routes in Given the functional properties and lightness of the Manufacturing shown. The expression “typical chemical formula "a chemical formula of the main product which based on a given structure of a starting material, because industrial products used as raw materials such as epoxy resins inevitably have some amounts of by-products, such as isomers, and reaction products of excess epichlorohydrin, partially saponified epoxy resins and the like used in the epoxy resins are included. This connection includes a wide variety of structures and of it can the most suitable structure and the most suitable synthetic route are selected.

The compound represented by the general formulas (1) to (6), which is the base material for composing the composition of the present invention, is in the composition as one Contain material for forming an ink receiving layer. The content of the compound in the ink receiving layer is not particularly limited, provided that functions such as ultraviolet curability, dye fixability of the ink receiving layer and the like can be realized from the compound. The optimal component ratio in the composition can be selected depending on the intended performance and the film formation process used.

However, to provide adequate functions can be achieved by connecting the general formulas (1) to (6) in the composition containing not less than 25 % By weight more preferably not less than 50% by weight, still further preferably contain from 55 to 98% by weight.

polymerization

The composition of the present The invention can furthermore contain an initiator, which can be activated Energy rays can be activated. If such a polymerization initiator with a cationic polyacryloyl compound from any of the general formulas (1) to (6) is mixed, a solid polymer layer, this means an ink receiving layer in a short time by exposure across from ultraviolet light or other active energy rays become.

This polymerization initiator includes:
1-hydroxycyclohexyl phenyl ketone,
2-hydroxy-2-methyl-1-phenylpropane-1-one,
1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one;
Acetophenones such as

2,2-diethoxyacetophenone,
2,2-dimethoxy-2-phenyl,
2-hydroxy-2-methyl-1-phenylpropane-1-one,
2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1,4-phenoxydichloroacetophenon,
4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone,
pt-Butyldichloroacetophenon,
pt-butyltrichloroacetophenone, and
p-dimethylaminoacetophenone;
Benzoin ethers such as
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and benzyl dimethyl ketal;
Benzophenones, such as
Benzophenone, benzophenone methyl ether, benzoylbenzoic acid, methylbenzoylbenzoate, hydroxybenzophenone, 4-phenylbenzophenone,
3,3'-dimethyl-4-methoxybenzophenone,
3,3'-bis (N, N-dimethylamino) benzophenone,
4,4'-bis (N, N-diethylamino) benzophenone,
4 ', 4''- Diethylisophthalophen,
3,3 ', 4,4'-tetra (t-butyloxycarbonyl) benzophenone,
4-benzoyl-4'-methyldiphenyl sulfide and acrylated benzophenone;
Xanthones such as thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-isopropylthioxanthone, 2-chlorothioxanthone and 2,4-dichlorothioxanthone;
Diketones such as diacetyl and benzyl;
Quinones, such as 2-ethylanthraquinone,
2-t-butylanthraquinone, 2,3-diphenylanthraquinone, 1,2-benzanthraquinone, octamethylanthraquinone, camphorquinone, dibenzosuberone and 9,10-phenanthrenequinone. Furthermore, CGI 1700 and CGI 149 (trade names, bisacylphosphine oxide-based mixtures manufactured by Japan Ciba Geigy Co.), which are sensitive to visible light and useful as an initiator in a white pigment system, are useful for a dispersion system.

The polymerization initiator will preferably used in an amount ranging from about 1 to approximately 10 parts by weight is sufficient based on 100 parts by weight of the connection of the general formulas (1) to (6). If a connection in combination is used, which differs from that of the general formulas (1) to (6) differs, the polymerization initiator in an amount of 1 to 10 parts by weight based on the total Solid matter used.

photopolymerizable Acrylic compound

The composition for an ink receiving layer of the present invention may further be one contain photopolymerizable compound with two or more acryloyl groups but without a cationic group in one molecule, that is, a known photopolymerizable acrylic compound. Such a known photopolymerizable acrylic compound has no dye fixing property since it does not have a cationic group, but is for adjusting a hydrophilicity-hydrophobicity value of the solid layer (ink receiving layer) itself, improving the adhesion of the layer to the base material, adjusting the film properties such as Hardness and flexibility of the solid layer, useful. When the ink-receiving layer is formed by using only a cationic polymerizable compound having a non-cationic group, the layer becomes excessively hydrophilic, which tends to cause the base material to wind up. The use of a photopolymerizable compound of acrylic acid type without a cationic group in combination is effective for setting such properties.

The photopolymerizable acrylic compound includes (meth) acrylic acid ester of polyhydric alcohols, glycols, polyethylene glycols, polyester polyols, Polyether polyols, and urethane-modified polyethers or polyesters; and (meth) acrylate esters of epoxy resins.

Specific examples of these include:
Ethylene glycol di (meth) acrylate, propanediol di (meth) acrylate,
Butanediol di (meth) acrylate, pentanediol di (meth) acrylate,
Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Neopentylglycolhydroxypivalatdi (meth) acrylate;
Polyethylene glycol di (meth) acrylate,
Polypropylenglycald (meth) acrylate,
Polytetrafuranglycoldi (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and
Pentaerythritol tetra (meth) acrylate; (Meth) aerylate esters of polyesters or polyurethanes, such as Arronix M-1100, Arronix M-1200, Arronix M-6100, Arronix M-6200, Arronix M-6250, Arronix M-6300, Arronix M-6400, Arronix M-7100 , Arronix M-8030, Arronix M-8100 (Arronix: trade name, manufactured by Toagosei Chemical Industry Co.), Kayarad DPCA-120, Kayarad DPCA-20, Kayarad DPCA-30, Kayarad DPCA-60, Kayarad R-526, Kayarad R-629 and Kayarad R-644 (Kayarad: trade name, manufactured by Nippon Kayaku Co., Ltd.).

Specific examples of the above photopolymerizable compound without a cationic group, which of Epoxy resins include: (meth) acrylate esters from Compounds with two or more epoxy groups in the molecule, such as 1,6-Hexandioldiglycidyletherdi (meth) acrylate, Trimethylolpropane triglycidyl ether tri (meth) acrylate, glycerol triglycidyl ether tri (meth) acrylate, Isocyanursäuretriglycidylethertri (meth) acrylate, (Meth) acrylate of novolak-type epoxy resins and (meth) acrylic acid esters from a disphenol-type epoxy resin: DENAKOL Acrylate DM-201, DM-811, DM851, DM-832, DA-911, DA-920, DA-931, DA-314, DA-701, DA-721 and DA-722 (DENAKOLe: trade names) by Nagase Kasei Kogyo K.K.).

The photopolymerizable acrylic compound without a cationic group is preferably used in an amount of 10 up to 200 parts by weight per 100 parts by weight of a compound of general formulas (1) to (6) are used.

In addition to the above polyfunctional monomer can be a monofunctional monomer with a tertiary Amino group or a quaternary Ammonium group in the composition for the purpose of reduction the viscosity to be built in. The monomer contains the quaternary compounds of a monofunctional acrylic acid monomer with a tertiary Amino group used in route 1 for cation introduction becomes.

water-soluble polymer

The composition of the present The invention can also be a water-soluble polymer for adjustment the ink absorbency and the ink absorption rate of the ink receiving layer. The water-soluble Polymer in particular includes commercially available water-soluble or water-swelling polymers, such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl formal, polyvinyl butyral, gelatin, Carboxymethyl cellulose, hydrooxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl starch, Polyethyloxazoline, polyethylene oxide, polyethylene glycol, polypropylene oxide and block copolymer of ethylene oxide and propylene oxide.

Of these, the following are particularly preferred: Polyvinyl alcohol, cationized polyvinyl alcohol, cationized Strength, water-soluble Resins with a canonical monomer unit with a ratio of 15 mol% or more, polyacrylamides, poly-N-vinylpyrrolidone, polyethylene oxide, and block copolymers of polyethylene oxide and polypropylene oxide.

The water soluble polymer is preferred contained in an amount of 5% to 50% by weight of the composition.

Examples of the solvent for the composition curable with active energy rays used in the present invention are water, water-miscible polar solvents such as: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, isopropyl alcohol, N-methyl-2-pyrrolidone, methyl ethyl ketone, acetone, tetrahydrofuran, acetonitrile and the like, and mixtures thereof.

Examples of mixed solvents are a mixture of water and isopropyl alcohol (50: 50% by weight), a mixture of ethylene glycol monomethyl ether and isopropyl alcohol (50: 50% by weight), a mixture of ethylene glycol monoethyl ether and methyl ethyl ketone (60:40 wt.%), a mixture of N-methyl-2-pyrrolidone and water (70:30 wt.%), a mixture of water and acetonitrile (50: 50% by weight) and the like.

Fine particulate material

When making an ink jet recording paper sheet by using the composition of the present invention can be a conventional fine-particulate Material or white Pigment with a high void ratio in the composition for the purpose of improving ink absorbency (Absorption rate and capacity) or awarding a degree of whiteness be dispersed. The fine particulate material contains Particles of inorganic material, such as silicon dioxide, magnesium carbonate, Alumina, talc, clay and titanium oxide; Particles from organic Material such as acrylic resins, styrene resins, silicone resins, vinyl resins, Fluororesins and urea resins. The fine particulate material is preferably from 3% to 30% by weight of the composition contain.

Procedure for Production of the recording medium

The recording medium of the present Invention is made by the composition of the present Invention on a base material, for example non-absorbent Base material, applied or applied and this before Hardened inkjet printing becomes. The application of the composition to the base material can by any conventional Application devices, such as a whirling device, a roller coating device, a spray coating device, and a screen printer. After the application becomes the coating layer by evaporation of the solvent dried if necessary and is by polymerization by irradiation with active energy rays, such as electron beams and ultraviolet rays.

The composition of the present Invention is not just on paper sheets and plastic films but also on non-absorbent base materials, such as metal plates, Plates and shaped objects made of plastics, rubbers, ceramics, fabrics, leather, glass plates and food packaging materials applicable to these ink receiving properties to rent. The procedure for applying the composition includes Roller coating, screen printing, gravure printing, offset printing, spin coating, spray coating, Immersion coating and beam coating; and transmission of a separately made film. In principle is an ink jet process also to apply the composition with a solvent for a viscosity diluted by 5 cP or less is practicable on the base material. In the case where the above application of the composition not without a solvent is practical, the composition can be mixed with water, an alcohol, an acetate ester, a ketone or the like as the solvent dilute become.

support film for overhead projector

The composition of the present Invention is for the production of the overhead projector sheet (OHP film) useful, because the composition is transparent and has an excellent ink absorption capacity and has ink fixability. The backing material for the OHP sheet is preferably a film used in graphic art such as polyethylene terephthalate, cellulose acetate, polycarbonate, Polyvinyl chloride, polystyrene, polysulfone and aliphatic polyester film.

The present invention is as follows in greater detail are described using examples. In the description below is the unit "part" by weight unless otherwise stated.

synthesis example

welche zu den Verbindungen der allgemeinen Formel (1) gehört, wurde gemäß der vorstehend erwähnten Syntheseroute 1 synthetisiert.The compound (1-6) of the formula given as an example

which belongs to the compounds of the general formula (1) was synthesized according to synthesis route 1 mentioned above.

wurden 10 g Ethylalkohol und 50 ml Wasser als Katalysatoren zugegeben. Hierzu wurde 75 g (ungefähr 0,5 mol) M,N-Dimethyl-2-Hydroxypropylacrylamid zugegeben, und die Mischung wurde gleichförmig in einen Druckreaktor gerührt. Dann wurde die Mischung bei ungefähr 75°C für 20 Stunden unter Rühren in dem festverschlossenen Reaktor erhitzt. Nach Vervollständigung der Reaktion wurden Wasser und nicht umgesetztes N,N-Dimethyl-2-hydroxypropylacrylamid unter einen verminderten Druck entfernt, um das Produkt (1-6) als eine viskose Flüssigkeit (Wassergehalt: 15%) zu erhalten.To 140 g of polyethylene glycol diglycidyl ether (epoxide equivalent: 284, added ethylene oxide units: about 9 moles, DENAKOL EX-832, trade name, manufactured by Nagase Kasei Kogyo KK; molecular weight for n = 9: 526) of the typical structure

10 g of ethyl alcohol and 50 ml of water were added as catalysts. To this was added 75 g (approximately 0.5 mol) of M, N-dimethyl-2-hydroxypropylacrylamide and the mixture was stirred uniformly in a pressure reactor. Then the mixture was heated at about 75 ° C for 20 hours with stirring in the sealed reactor. After the completion of the reaction, water and unreacted N, N-dimethyl-2-hydroxypropylacrylamide were removed under a reduced pressure to obtain the product (1-6) as a viscous liquid (water content: 15%).

The average double bond equivalent of the resulting product was converted from the weight of the Bromide calculated, and the cation equivalent was determined using a Colloid titration measured with potassium polyvinyl sulfonate. The results are shown below. In the description below means the expression "double bond equivalent" the molecular weight per double bond, and the expression "cation equivalent" means the molecular weight per a cationic group.

Table 1

DENAKOL EX-832, the. As the raw material is an industrial material, and has one Distribution of moles of ethylene oxide added among the molecules. Out the previous reason found that two double bonds and two cationic groups were introduced on average.

The disappearance of the epoxy group and the formation of the cationic group in the DENAKOL EX-832, the starting material, were confirmed by ¹ H-NMR and ¹³ C-NMR as indicated below.

1. ¹ H-NMR determined that the starting material had the spectrum of the methylene group -CH-CH _{2 of} the end glycidyl group with a chemical shift of δ = 2.5-3.0, whereas it was found that the reaction product was not the spectrum in this chemical shift.

2. The tertiary amine monomer (N, N-dimethyl-2-hydroxypropylacrylamide), another starting material, had a spectrum belonging to N-CH ₃ with a chemical shift of δ = 2.3-2.8, whereas it was found in the product that the chemical shift occurred at δ = 3.2-3.3, which belonged to the spectrum of the tertiary ammonium group N ⁺ CH ₃ .

3. Using ¹³ C NMR, the product was found to have a peak belonging to N ⁺ CH ₃ at δ = 52-53.

As shown above the results of the measurement of the bromide number (i.e. double bond equivalent), Colloidal titration (i.e. Cation equivalent) and NMR, which is the reaction in the synthesis reaction in this example as required advance to form the intended connection.

Synthesis example 2

welche zu den Verbindungen der allgemeinen Formel (5) gehört, wurde gemäß der vorstehend erwähnten Syntheseroute 2 hergestellt.The compound (2-5) of the formula shown as an example

which belongs to the compounds of the general formula (5) was prepared according to synthesis route 2 mentioned above.

wurden 20 g Ethylalkohol und 100 g Wasser als Katalysatoren gegeben. Darin wurde 195 g (1 Mol) Trimethylaminhydrochlorid aufgelöst, um eine Reaktionsmischung zu bilden. Diese wurde gleichförmig in einem Druckreaktor auf die gleiche Weise wie in Synthesebeispiel 1 vermischt. Dann wurde die Mischung bei ungefähr 60°C für 15 Stunden in dem fest verschlossenen Reaktor unter Rühren erhitzt. Nach Vervollständigung der Reaktion wurden Wasser und nicht umgesetztes Trimethylaminhydrochlorid unter vermindertem Druck entfernt, um das Produkt als eine viskose Flüssigkeit zu erhalten. Das resultierende Intermediat besaß ein Epoxidäquivalent von 530. 250 g dieses Intermediats im Bezug auf die reine Substanz wurde mit 40 g Acrylsäure vermischt, und die Mischung wurde bei 80°C unter Entfernung des gebildeten Wassers unter Rückfluss für 6 Stunden umgesetzt, um die Veresterung des Intermediats zu vervollständigen. Nach der Vervollständigung der Reaktion wurde das resultierende Produkt in Wasser aufgelöst. Wasser und nicht umgesetzte Acrylsäure wurden bei 50°C unter vermindertem Druck entfernt, um das beabsichtigte Produkt zu erhalten.To 350 g (about 2 epoxy equivalents) of polyglycerol polyglycidyl ether (epoxy equivalent: 173, DENAKOL EX-512, trade name, manufactured by Nagase Kasei Kogyo KK; n is about 2) with the typical structure

20 g of ethyl alcohol and 100 g of water were added as catalysts. Therein, 195 g (1 mole) of trimethylamine hydrochloride was dissolved to form a reaction mixture. This was mixed uniformly in a pressure reactor in the same manner as in Synthesis Example 1. Then the mixture was heated at about 60 ° C for 15 hours in the sealed reactor with stirring. After the completion of the reaction, water and unreacted trimethylamine hydrochloride were removed under reduced pressure to obtain the product as a viscous liquid. The resulting intermediate had an epoxide equivalent of 530. 250 g of this intermediate in terms of the pure substance was mixed with 40 g of acrylic acid, and the mixture was reacted at 80 ° C to remove the water formed under reflux for 6 hours to esterify the To complete intermediates. After the completion of the reaction, the resulting product was dissolved in water. Water and unreacted acrylic acid were removed at 50 ° C under reduced pressure to obtain the intended product.

The final product contained water with a content of 12%. The product was subjected to measurement of the bromide value and the cation equivalent. The results are shown below. Table 2

The compound of this Synthesis Example 2 was subjected to proton NMR and ¹³ C-NMR measurement, and it was confirmed that the quaternary ammonium group was formed in the same manner as in Synthesis Example 1.

Synthesis example 3

welche zu den Verbindungen der allgemeinen Formel (4) gehört, wurde gemäß der vorstehend erwähnten Syntheseroute synthetisiert.The compound (3-4) of the formula shown as an example

which belongs to the compounds of the general formula (4) was synthesized according to the above-mentioned synthetic route.

besitzt.Trimethylolpropane triacrylate (trade name: Arronix, manufactured by Toagosei Chemical Co., Ltd.) was used as the starting material, which is a photopolymerizable oligomer with three acryloyl groups, and the chemical structure with the formula

has.

300 g (approximately 1 mol) of this trimethylolpropane triacrylate was with 32 g (approx 1/3 mol) of trimethylamine hydrochloride under a nitrogen atmosphere at 50 ° C with violent stir implemented to get the product.

This end product (3-4) became the Measurement of the bromide number and the cationic equivalent subjected. The Results are shown below.

Table 3

Synthesis example 4

welche zu den Verbindungen der allgemeinen Formel (4) gehört, wurde gemäß der vorstehend erwähnten Syntheseroute 4 synthetisiert.The compound (4-1) represented by the example with the formula

which belongs to the compounds of the general formula (4) was synthesized according to synthesis route 4 mentioned above.

Glycerol triglycidyl ether (trade name: DA-314, manufactured by Nagase Kasei Kogyo KK; molecular weight: 476) was used as the starting material, which is an acrylate ester of an epoxy resin, with the typical chemical structure of the formula

To 48.0 g of this glycerol triglycidyl ether aerylate ester (DA-314) became 60 g (approx 0.14 mol) 2,3-Epoxidpropyltrimethylammoniumchlorid (Trade name: Wisetex E-100, a cationizing agent), The mixture was at 70 ° C for 8 hours touched, to introduce a cation into part of the DA-314 hydroxyl groups. There this DA-314 has more hydroxyl groups as the reactive site in the molecule (two or three hydroxyl, 2.4 on average), that is Product of course a mixture.

This final product (4-1) was subjected to measurement of the bromide number and the cation equivalent in the same manner as in Synthesis Example 1. The results are shown below. Table 4

Synthesis example 5

welche zu der Verbindung der allgemeinen Formel (6) gehört, wurde gemäß der vorstehend erwähnten Syntheseroute 2 wie folgt synthetisiert.The compound (2-7) of the formula shown as an example

which belongs to the compound of the general formula (6) was synthesized according to the above-mentioned synthesis route 2 as follows.

Sorbitol polyglycidyl ether (epoxy equivalent: 170, trade name: DENAKOL EX-611, manufactured by Nagase Kasei Kogyo K.K.) was used as the starting material. According to the reaction route 2, 340 g of this EX-611 was successful with 0.5 mol of trimethylamine hydrochloride and 1.5 moles of acrylic acid implemented to get the product.

This product (2-7) was the measurement the bromide number and the cation equivalent subjected in the same manner as in Synthesis Example 1. The Results are shown below.

Table 5

Synthesis example 6

welche zu den Verbindungen der allgemeinen Formel (2) gehört, wurde gemäß der vorstehend erwähnten Syntheseroute 1 wie folgt synthetisiert.The compound (1-7) of the formula shown as an example

which belongs to the compounds of the general formula (2) was synthesized according to the above-mentioned synthesis route 1 as follows.

trimethylolpropane (Epoxy equivalent: 145, trade name: DENAKOL EX-321, manufactured by Nagase Kasei Kogyo K.K.) was used as the starting material. 290 g of this EX-321 was made with 314 g of N, N-dimethylaminoethyl methacrylate implemented to acrylic acid cation groups in the same way as in Synthesis Example 1 to introduce to get the product.

This product (1-7) was subjected to measurement of the bromide number and the cation equivalent in the same manner as in Synthesis Example 1. The results are shown below. Table 6

Synthesis example 7

welche zu den Verbindungen der allgemeinen Formel (3) gehört, wurde gemäß der vorstehend erwähnten Syntheseroute 1 synthetisiert.The compound (1-8) of the formula shown as an example

which belongs to the compounds of the general formula (3) was synthesized according to synthesis route 1 mentioned above.

pentaerythritol polyglycidyl ether (Epoxy equivalent: 231, trade name: DENAKOL EX-411, manufactured by Nagase Kasei Kogyo K.K.) as the starting material was treated with N, N-dimethylaminopropyl acrylate according to the synthesis route 1 implemented to get the product.

This product (1-8) was the measurement the bromide number and the cation equivalent subjected in the same manner as in Synthesis Example 1. The Results are as shown below.

Table 7

example 1

A composition that consists of the following components: Compound (1-6) (Synthesis Example 1) 97 parts 2-Hydroxy-2-methyl-1-phenyl-1-one (Irgacure 1173, manufactured by Japan Ciba Geigy Co.) 3 parts isopropyl alcohol 15 parts
was produced. This composition was applied to a polyethylene terephthalate film 85 µm thick by a bar coater, and the applied composition was dried at 70 ° C for 3 minutes to form a layer of approximately 10 µm in dry thickness. This film was exposed to ultraviolet rays from a high pressure mercury lamp with an integrated dose of 150 mJ / cm ² (amount of light at about 365 nm) to cause polymerization to form an ink receiving layer.

Pieces from this film were made each in the six types of water-based ink jet recording color solutions (dye concentration: 8% to 10% by weight) each immersed to six specimens for 60 seconds manufacture. The film pieces after immersion in the dye solutions were washed off with water and dried to six pieces of film in the transparent dark colored Preserve condition. The colored ones film pieces were well colored without flooding of dyes by further washing with water.

Schwarzer Farbstoff der Formel

und Magentafarbstoff der Formel

Dyes used for dyeing:
CI Food Black 2,
CI Direct Blue 199,
CI Direct Bellow 86,
Black dye of the formula

Black dye of the formula

and magenta dye of the formula

Example 2

A composition consisting of the following components: Compound (2-5) (Synthesis Example 2) 70.0 parts Polyethylene glycol 400 diacrylate 30.0 parts Irgacure 184 4.0 parts isopropyl alcohol 40 parts was produced. This composition was applied to a polyethylene terephthalate film 85 µm thick by a bar coater to form a layer of approximately 15 µm in dry thickness. This film was exposed to ultraviolet rays from a high pressure mercury lamp with an integrated dose of 200 mJ / cm ² to cause polymerization to form an ink receiving layer.

Pieces from this film were made on coloring with inkjet inks using the dyes in the example 1 were tested in the same manner as in Example 1, except that the ink solvent a mixture of water, thiodiglycol, urea and isopropyl alcohol in a ratio of 80: 10: 5: 5 by weight and dye concentration 3% by weight. As a result, the film pieces showed excellent dye fixing properties and attachment.

Example 3

A composition consisting of the following components: Compound (3-4) (Synthesis Example 3) 60.0 parts Kayarad DPCA 30 (manufactured by Nippon Kayaku Co.) 30.0 parts Cation-modified PVA (degree of cationization: 10%, molecular weight: 1.5 × 10 ⁴ , aqueous 20% solution) 50.0 parts Irgacure 651 3.5 parts was produced. This composition was applied to a 100 µm thick polyethylene terephthalate film by a bar coater and dried at 80 ° C for 10 minutes in an air oven to form a layer of about 15 µm in dry thickness. This film was cured by exposure to ultraviolet rays at an integrated dose of 200 mJ / cm ² .

Inkjet printing was done on this film manufactured with a BJC-600J color ink jet printer (trade name carried out by Canon K.K.), around isolated monochrome patterns of 2 cm × 2 cm each of seven colors black, yellow, cyan, magenta, red, blue and green print. As a result became a distinctive Color chart formed, with each pattern a sharp outer boundary without bleeding ink.

Example 4

A white dispersion was prepared by dispersing the following components using an ultra-homogenizer at 8000 rpm for 15 minutes: Compound (4-1) (Synthesis Example 4) 70.0 parts Epoxy acrylate DA314 (manufactured by Nagase Kasei Kogyo KK) CGI 1700 (photopolymerization initiator manufactured by Japan Ciba Geigy Co.) 4.0 Titanium oxide (CR-50, manufactured by Ishihara Sangyo KK) 7.0 parts Dispersant (monoethanolamine salt of Phosphanol RE610 manufactured by Toho Chemical Industry Co.) 1.0 parts water 70.0 parts isopropyl alcohol 30.0 parts

This dispersion was applied to a polycarbonate plate by means of a wide coating device in a thickness of 15 μm. The applied dispersion layer was cured by irradiation with ultraviolet rays at an integrated dose of 300 mJ / cm ² . Color printing was carried out on this substrate with the same color ink jet printer as in Example 3. As a result, the printed matter obtained had excellent ink absorbency, color filling and waterfastness. In particular, the color reflection density was excellent because the ink receiving layer was white.

Example 5

The following components were treated for the dispersion in the same manner as in Example 4 to prepare a white photosensitive dispersion: Compound (2-7) (Synthesis Example 5) 70.0 parts Epoxy acrylate DA314 30.0 parts CGI 1700 4.0 parts Titanium oxide (CR-50) 7.0 parts Dispersant (monoethanolamine salt of Phosphanol RE 610) 1.0 parts

To 100 parts of this dispersion, 50 parts of an aqueous 20% solution of cationized PVA (degree of cationization: 10%, molecular weight: 1.5 × 10 ⁴ ) was added to prepare a water-based paint.

This paint was on an unsaturated polyester plate applied by a roller coating device in a thickness of 10 μm. The hardened Platte had one dry surface and was in an easily storable condition. The applied layer was cured with a transportation type UV curing device that a high pressure mercury lamp with 80 W / cm with a line hardening rate of 2 m / min. On this white one Plate became an artificial one Glass ball pattern printed with a color inkjet printer. The Print was stable in an ink receiving characteristic.

Example 6

The components: Titanium oxide (CR-50) 25 parts Aqueous 20% solution from a copolymer of Tyrol, acrylic acid and acrylonitrile (monomer ratio: 50: 30: 20, based on the weight, molecular weight: 6500) 30 parts water 150 pieces isopropyl alcohol 10 parts were mixed well. The mixture was treated with glass beads for dispersion with a 200 ml sand mill to prepare an aqueous titanium oxide dispersion having a solid content of 206.

The following components were added to 100 parts of this dispersion to prepare an aqueous photosensitive white color composition: Compound (1-7) (Synthesis Example 6) 80 parts cationized starch (aqueous 25% solution, degree of cationization: 10%) 80 parts.

This color composition was based on an uncoated paper sheet (normal paper sheet) with a thickness of 100 μm applied to a wire bar to give a dry coating thickness of 25 μm to have, and was at 70 ° C. for 10 Minutes in the oven. The coating layer was through Polymerization with the same UV radiation device as in the Example 5 hardened.

On the resulting coated Paper became a print test pattern including letters, printed images and drawings printed. As a result, the color inks became sufficient fixed to form a sharp color print. After printing became water over the printed matter speckled to the waterfastness of the printed Test picture. It was found that water justice was sufficient without bleeding out of the dye.

Example 7

A composition consisting of the following components: Compound (1-8) (Synthesis Example 7) 96 parts Irgacure 184 4 parts Ethylene glycol monoethyl ether 30 parts
were applied to a glass base plate by a spinner in a dry thickness of 3 µm. The applied composition was photopolymerized by exposure to ultraviolet rays for 30 seconds using a 500 W extra high pressure mercury lamp. A mosaic pattern was printed on this plate using inkjet inks using red (r), green (g), and blue (b) colors. After printing, the printed matter was dried at 120 ° C for 5 minutes to evaporate the solvent to dryness. The resulting filter glass had an excellent transmitted color density and sharpness of the image and had an outstanding waterfastness compared to a subsequent washing treatment.

Example 8

A recording medium was prepared in the same manner as described in Example 3, except that the composition consisted of the following components: Connection (4-1) 25 parts Blenmer AB-350 (polyethylene glycol monoacrylate (n = 6 to 8); manufactured by Nippon Yushi Co.) 25 parts dimethylaminoethyl 40 parts hydroxyethyl 10 parts CGI 1700 3.5 parts (Photopolymerization initiator manufactured by Japan Ciba Geigy Co.) a mixture of water and isopropyl alcohol (50:50 by weight) 50 parts was used in place of the composition of Example 1. Color printing was carried out in the same manner as described in Example 3. As a result, the same effect as in Example 3 was obtained.

Example 9

A recording medium was prepared in the same manner as described in Example 3 except that a composition composed of the components Connection (3-2) 40 parts N-methylolacrylamide 20 parts PEG 200 diacrylate 20 parts Polyvinyl pyrrolidone (PVP K-90; manufactured by ISP Technologies) 20 parts Irgacure 184 (photopolymerization initiator manufactured by Japan Ciba Geigy Co.) 4 parts and a mixture of water and isopropyl alcohol (50:50 by weight) 50 parts was used instead of the composition of Example 3.

Color printing was done on the same Way as outlined in Example 7. As a result, the same effect as in Example 3 was obtained.

As described above, the present invention a curable Provide composition for making inkjet paper sheets and OHP films is suitable, in particular a resin composition and a recording medium using this, which adapts to performance of ink jet color printing that has been widely used recently are adapted, and which additional good dyeing ability Meet requirements, that (1) an ink receiving layer is formed by a short treatment time can, (2) the layer formed has high adhesion to the Has base material, (3) ink can be fixed in a short time can by exposing to active energy rays is hardened (4) the layer of high affinity with coloring matter (dye or pigment) in the ink, (5) sharp images with high resolution can be formed (6) the resin layer has high durability, etc., especially high absorbency for on It shows water-based ink and a high affinity for coloring matter.

Claims (47)

An active energy ray curable composition comprising: a cationic polyacryloyl compound having two or more acryloyl groups and one or more cationic groups in one molecule represented by any of the general formulas (1) to (6) and (2-1 ), (2-3), (2-6) is shown:

where Z ₁ to Z ₆ independently represent a radical which is derived from a polyhydric alcohol or a polyepoxide, K ₁ independently represents a radical of the formula

represents K _{2 is} a radical of the formula

R ₁ independently represents a radical of the formula

represents, wherein R _{3 is} independently H- or CH ₃ - and R _{2 is} independently a radical of the formula CH ₂ = CHCOO ^- or CH ₂ = C (CH3) COO ^- represents,

Composition according to claim 1, the composition comprising the polyacryloyl compound with a Content of not less than 25% by weight. Composition according to claim 1, the composition comprising the polyacryloyl compound with a Content of not less than 50% by weight. Composition according to claim 1, the composition comprising the polyacryloyl compound with a Content ranging from 55 wt% to 98 wt%. The composition of claim 1, wherein the acryloyl compound is selected from the compounds of formula (a) to (g):

Composition according to claim 1, the composition further comprising a polymerization initiator includes which can be activated by active energy rays. Composition according to claim 6, the composition of the polymerization initiator in one Quantity of 1 to 10 parts by weight based on 100 parts by weight the polyacryloyl compound. Composition according to claim 1, wherein composition further comprises a photopolymerizable compound with two or more acryloyl groups but not cationic Group includes. Composition according to claim 8, the photopolymerizable compound being selected from the group those from (meth) acrylic acid esters of polyhydric alcohols, glycols, polyethylene glycols, polyester polyols, Polyether polyols, and urethane-modified polyethers or polyesters; and (meth) acrylate esters of epoxy resins. Composition according to claim 8, wherein composition is the photopolymerizable compound in an amount of 10 to 200 parts by weight based on 100 parts by weight of the polyacryloyl compound. Composition according to claim 1, wherein the composition further comprises a water-soluble polymer. Composition according to claim 11, the water soluble Polymer selected from the group is made of polyvinyl alcohol, cationically modified polyvinyl alcohol, cationized starch, water-soluble Resins with a cationic monomer unit with a ratio of 15 mol% or more, polyacrylamides, poly-N-vinylpyrrolidone, polyethylene oxide, and block copolymers of polyethylene oxide and propylene oxide. Composition according to claim 11, the composition of the water-soluble polymer in an amount from 5% to 50% by weight of the composition. Composition according to claim 1, the composition further comprising a white pigment dispersed therein includes. Composition according to claim 14, the composition of the white pigment in an amount of 3% to 30% by weight of the composition. A composition according to any one of claims 1 to 15, the composition further comprising a hydrophilic reactive diluent selected from dimethylaminoethyl acrylate, N-methylolacrylamide and Blenmer ^® AB-350. A method of making as a recording medium, comprising: applying a composition that is curable by active energy rays to a base material, and irradiating the composition with activating energy rays, the composition comprising a cationic polyacryloyl compound having two or more acryloyl groups and one or more cationic groups in comprises a molecule represented by one of the general formulas (1) to (6) and (2-1), (2-3), (2-6):

where Z ₁ to Z ₆ independently represent a radical which is derived from a polyhydric alcohol or a polyepoxide, K ₁ independently represents a radical of the formula

represents K _{2 is} a radical of the formula

R ₁ independently represents a radical of the formula

represents, wherein R _{3 is} independently H- or CH ₃ - and R _{2 is} independently a radical of the formula CH ₂ = CHCOO ^- or CH ₂ = C (CH ₃ ) COO ^- represents,

Method according to claim 17, wherein composition contains the polyacryloyl compound of not less than 25% by weight. Method according to claim 17, wherein composition contains the polyacryloyl compound of not less than 50% by weight of the composition. Method according to claim 17, wherein composition contains the polyacryloyl compound from 55% to 98% by weight. Method according to claim 17, the composition further comprising a polymerization initiator includes which can be activated by active energy rays. Method according to claim 21, wherein composition the polymerization initiator in a Quantity of 1 to 10 parts by weight based on 100 parts by weight the polyacryloyl compound. Method according to claim 17, wherein composition further comprises a photopolymerizable compound with two or more acryloyl groups but without a cationic group includes. Method according to claim 23, the photopolymerizable compound being selected from the group those from (meth) acrylic acid esters of polyhydric alcohols, glycols, polyethylene glycols, polyester polyols, Polyether polyols and urethane modified polyethers or polyesters; and (meth) acrylate esters of epoxy resins. Method according to claim 23, wherein the composition is the photopolymerizable compound in an amount of 10-200 Parts by weight based on 100 parts by weight of the polyacryloyl compound, includes. Method according to claim 17, the composition further being a water soluble Polymer includes. Method according to claim 26, the water soluble Polymer selected from the group is made of polyvinyl alcohol, cationically modified polyvinyl alcohol, cationic strength, water-soluble cationic resins with a cationic monomer unit at one relationship of 15 mol% or more, polyacrylamides, poly-N-vinylpyrrolidone, Polyethylene oxide, and block copolymers of polyethylene oxide and propylene oxide consists. Method according to claim 17, wherein the base material is not ink-absorbent. Method according to claim 28, wherein the base material is a plastic material. Method according to claim 17, the base material being a paper sheet. A recording medium comprising a base material and an ink-receiving layer formed thereon, the ink-receiving layer being a polymer of a cationic polyacylol compound having two or more acryloyl groups and one or more cationic groups in one molecule, represented by one of the general formulas (1) to (6) and ( 2-1), (2-3), (2-6) includes:

where Z ₁ to Z ₆ independently represent a radical which is derived from a polyhydric alcohol or a polyepoxide, K ₁ independently represents a radical of the formula

represents K _{2 is} a radical of the formula

R ₁ independently represents a radical of the formula

represents, wherein R _{3 is} independently H- or CH ₃ - and R _{2 is} independently a radical of the formula CH ₂ = CHCOO ^- or CH ₂ = C (CH ₃ ) COO ^- represents,

Recording medium according to claim 31, the ink-receiving layer containing the polyacryloyl compound containing not less than 25% by weight of the ink receiving layer includes. Recording medium according to claim 31, the ink-receiving layer containing the polyacryloyl compound containing not less than 50% by weight of the ink receiving layer includes. Recording medium according to claim 31, the ink-receiving layer containing the polyacryloyl compound a content of 55% by weight to 98% by weight of the ink-receiving layer. Recording medium according to claim 31, the ink receiving layer further comprising a polymerization initiator comprises, which can be activated by active energy radiation. Recording medium according to claim 31, wherein the ink receiving layer is the polymerization initiator in an amount of 1 to 10 parts by weight based on 100 parts by weight the polyacryloyl compound. Recording medium according to claim 31, wherein the ink receiving layer further comprises a photopolymerizable Connection with two or more acryloyl groups but without cationic Group includes. The recording medium according to claim 37, wherein the photopolymerizable compound is selected from the group consisting of (meth) acrylic acid esters of polyhydric alcohols, glycols, polyethylene glycols, polyester polyols, and urethane-modified polyethers or polyesters; and (meth) acrylate esters of epoxy resins. Recording medium according to claim 37, the composition being the photopolymerizable compound Containing 10 to 200 parts by weight based on 100 Parts by weight of the polyacryloyl compound. Recording medium according to claim 37, the ink-receiving layer further being a water-soluble Polymer includes. Recording medium according to claim 40, the water soluble Polymer selected from the group is that of polyvinyl alcohol, cationic polyvinyl alcohol, cationic Strength, water-soluble Resins with a cationic monomer unit at a ratio of 15 mol% or more, polyacrylamides, poly-N-vinylpyrolidone, polyethelene oxide, and block copolymers of polyethylene oxide and propylene oxide. Recording medium according to claim 31, wherein the base material is not ink-absorbent. Recording medium according to claim 42, wherein the base material is a plastic material. Recording medium according to claim 31, the base material being a paper sheet. Image formation process that includes: Apply one on Water based ink on the recording medium that is claimed 31 is made known. Image formation method according to claim 45, wherein the ink is applied by an ink jet method. Image formation method according to claim 46, wherein the ink jet process is a bubble jet process.